Cationic latex as a carrier for bioactive ingredients and methods for making and using the same

ABSTRACT

This invention relates to latex compositions that incorporate at least one bioactive component such as an antibacterial or antifungal agent, and methods for making and using such latex compositions. The latex compositions disclosed herein can be prepared by the emulsion polymerization of the latex component monomers in the presence of the at least one bioactive component.

PRIOR RELATED U.S. APPLICATION DATA

This application is a continuation-in-part of U.S. patent applicationSer. No. 10/882,570, filed Jul. 1, 2004, which claims priority to U.S.Provisional Application Ser. No. 60/484,745, filed Jul. 3, 2003, each ofwhich is incorporated herein by reference in its entirety.

TECHNICAL FIELD OF THE INVENTION

This invention relates to the field of polymeric materials that can beused in combination with a wide variety of substrates, such as textiles,metal, cellulosic materials, plastics, and the like, and to the field ofbioactive/antimicrobial agents such as antibacterial and antifungalmaterials.

BACKGROUND OF THE INVENTION

The deposition of latex polymer coatings on solid substrates has longbeen utilized to impart certain end-use performance properties to thosesubstrates, such as hydrophobicity, strength, adhesive properties,compatibility, and the like. Depending upon the selection of thestarting monomers, surfactants, emulsion polymerization conditions, andother parameters, the deposited polymers can be designed to carry ananionic, a cationic, or an amphoteric charge, a feature which directlyinfluences coating performance. Further, the resulting latex polymer canbe blended with a range of other functional materials to impartadditional or enhanced features to the final coating material.

One particularly useful feature exhibited by cationic latex polymersdisclosed in U.S. Patent Application Publication No. 2005/0003163 istheir inherent antimicrobial characteristics. Cationic polymers can alsobe blended with compositions containing small molecule bioactivecompounds, species more typically associated with antimicrobialactivity, in order to enhance these properties. These antimicrobialcomponents are usually employed in relatively small amounts asformulating ingredients that are added after the polymer has been made.While such blends are useful, many practical issues remain in attemptsto enhance or control the extent of antimicrobial protection thesecompositions might afford. For example, such compositions and methodsand are often inadequate for providing long-term protection ofmaterials, especially in their antifungal properties. Methods to augmentor to more finely control the antimicrobial properties are also needed.Regulatory issues associated with introducing a new antimicrobialmaterial, namely the polymer, may be significant. Moreover, approachesto prolong or extend the effectiveness of the antimicrobial propertiesremain elusive.

Therefore, what are needed are new methods and approaches to impart andto enhance antimicrobial activity of latex polymers, as well as thecoatings and articles prepared therefrom. What are also needed aremethods to more closely manage the antimicrobial activity of suchmaterials, including approaches to extend the effectiveness of theirbioactivity.

SUMMARY OF THE INVENTION

This invention encompasses new methods and approaches to incorporatebioactive or antimicrobial ingredients such as antibacterial andantifungal agents into a latex, such that the antimicrobial propertiesof the latex can be enhanced and controlled. The present invention alsorelates to new types of bioactive cationic polymer latex materials. Inone aspect, this disclosure provides a method for incorporatingantimicrobial ingredients into a latex during the emulsionpolymerization process. Previously, antimicrobial agents have been addedto a latex after the polymerization process and in relatively smallamounts as preservatives for the latex product or for the end useapplication such as paints. The present invention allows the use ofhigher concentrations of a wide range of bioactive ingredients,including highly hydrophobic bioactive ingredients, which can be readilyincorporated into the latices such that the resulting latex particlesfunction as carriers for the active ingredients. The thoroughincorporation of an active ingredient in this manner can afford asubstantially homogeneous distribution of the additive and result insuperior and sustained performance compared to pre-made dispersions.

In one aspect of this invention, the emulsion polymerization is carriedout such that the bioactive agents are incorporated into the polymerduring the emulsion polymerization, typically by dissolving thebioactive component in a monomer stream. In this manner, the bioactiveagents can be at least partially encapsulated within the latex polymermatrix. One advantage provided by this process is the ability toincorporate or encapsulate large amounts of bioactive ingredients,including hydrophobic components, without substantially degrading thebioactive agent. In another aspect, this invention also provides atunable antimicrobial system based on a cationic latex that has someinherent antimicrobial properties, which also function as a carrier forat least one bioactive ingredient, and optionally further includinganother bioactive additive that can be blended with the laticesdisclosed herein. Thus, these latices can have a multifunctional purposesuch as providing binding, strength, and dispersion properties inaddition to being a carrier for an active functional ingredient, andoptionally constituting one component of a blended antimicrobialcomposition.

In one aspect, because the bioactive ingredients are typicallyincorporated into a latex during the emulsion polymerization process,these bioactive components can be at least partially encapsulated withinthe latex polymer matrix. In another aspect, the bioactive componentscan be substantially encapsulated within the latex polymer matrix. Whilenot intending to be bound by theory, it is believed that, by deliveringthe active ingredient to a desired end use application, the latexpolymer with the encapsulated bioactive ingredients can providesustained and controlled exposure of the bioactive ingredients to theenvironment in which they are deployed, thereby providing longer andmore effective protection to the product or the application. Moreover,because the bioactive cationic latices can be formed by existingemulsion polymerization processes, the polymerization methodsadvantageously allow for the preparation of high molecular weightpolymers.

In a further aspect, the methods disclosed herein also provide thepotential to adjust the antimicrobial behavior using a combination ofapproaches to deploy the antimicrobial agent. For example, highlytailored antimicrobial properties can be imparted to a product by bothincorporating the bioactive ingredient into a latex during the emulsionpolymerization process, and by combining the resulting latex productwith the same or different bioactive component in a blend. This approachallows antimicrobial properties to be selected and adjusted using thepolymer, the additive, or both, depending on the circumstances and theperformance required.

In yet a further aspect, the techniques disclosed herein can provide theability to encapsulate larger amounts of the active ingredient into alatex composition than are afforded by standard methods. For example,antimicrobial components are usually employed in relatively smallamounts as formulating ingredients once the latex polymer has beenprepared, and such bioactives typically are utilized at concentrationsranging up to about 1000-2000 ppm. In contrast, the antimicrobialcomponent of the latex compositions of this invention can be utilized inconcentrations as high as about 40 weight percent based on the totalmonomer weight. In this aspect, this invention can provide stable,concentrated dispersions that can be used as such, or as an additive, orconcentrated dispersions that can be diluted and added to other systemswhich require antimicrobial protection. High antimicrobial componentconcentrations provide flexibility and ensure the utility of these latexcompositions as concentrates as well as in non-concentrated form.

While the methods disclosed herein can be applied to any bioactive agentthat a particular end use requires, the present disclosure is primarilydrawn to providing or enhancing the antimicrobial properties of a latex,substrate, or particular end product. The relevant antimicrobialactivity can include antibacterial activity, antifungal activity,antiviral activity, antiparasitic activity, or any combination thereof,depending upon the particular selection of bioactive agents. As usedherein, the general term “bioactive” component, agent, or ingredient isused interchangeably with the term “antimicrobial” component, agent, oringredient.

In another aspect, this invention provides a bioactive cationic polymerlatex comprising:

-   -   a) a latex polymer comprising the polymerization product of: i)        at least one ethylenically unsaturated first monomer; and ii) at        least one ethylenically unsaturated second monomer that is        cationic or a precursor to a cation;    -   b) at least one bioactive component at least partially        encapsulated within the latex polymer; and    -   c) optionally, at least one sterically bulky component        incorporated into the latex polymer.        In this aspect, a wide range of weight percentages of        ethylenically unsaturated first monomer and ethylenically        unsaturated second monomer that is cationic or a precursor to a        cation, which can be referred to as the “cationic” monomer, can        be used. For example, the latex can comprise from about 0.01 to        about 75 weight percent of the cationic second monomer based on        the total monomer weight.

Also in this aspect, while the at least one sterically bulky componentincorporated into the latex polymer is an optional component, thisinvention also provides for use of a wide range of amounts andconcentrations of this component. Thus, as will be understood by theskilled artisan, in bioactive cationic polymer latices that do notincorporate at least one sterically bulky component, latex stability canbe enhanced by increasing the relative proportion of the cationic secondmonomer, by the addition of surfactants such as nonionic surfactants,and the like, including any combination of such methods. The relativeproportion of the cationic second monomer can be reduced and/orsurfactants can be eliminated in the presence of at least one stericallybulky component.

Further, the latices of this invention can also comprise a stericallybulky component which is incorporated into the cationic polymer latex tosterically stabilize the latex. These sterically bulky components caninclude, but are not limited to, monomers, polymers, and mixturesthereof as set forth below. Thus, a monomer can be incorporated as aco-monomer that can attach to, or constitute a portion of the backboneof the cationic polymer, examples of which include an alkoxylatedethylenically unsaturated third monomer. A polymer can be incorporatedby adsorbing or being grafted onto the latex surface, an example ofwhich includes polyvinyl alcohol.

In still another aspect, this invention provides a method of making abioactive cationic polymer latex comprising initiating an emulsionpolymerization of an aqueous composition comprising, at any time duringthe emulsion polymerization:

-   -   a) at least one ethylenically unsaturated first monomer;    -   b) at least one ethylenically unsaturated second monomer that is        cationic or a precursor to a cation;    -   c) at least one bioactive component;    -   d) at least one free-radical initiator;    -   e) optionally, at least one sterically bulky ethylenically        unsaturated third monomer;    -   f) optionally, at least one sterically bulky polymer; and    -   g) optionally, at least one nonionic surfactant.        Thus, in one aspect, the at least one bioactive component can be        dissolved in the monomer feed at any time during the emulsion        polymerization process. Further, in another aspect, the aqueous        composition components and the at least one bioactive component        can be provided as a dispersion prior to initiating the emulsion        polymerization. Thus, this invention provides for batch        processes, in which the at least one bioactive component is        present in the seed stage. In this aspect, the emulsion        polymerization is initiated when all the components of the        composition, including the at least one bioactive component, are        present from the time of initiation. Further, this invention        also provides for semi-continuous processes in which the        emulsion polymerization is initiated at a time when all        components of the composition are not present from the time of        initiation, but some are added at various times after initiating        the polymerization. In this aspect, for example, the at least        one bioactive component can be added at any time after the seed        stage. In another aspect, for example, any other component or        combination of components provided above can be added at any        time after the seed stage, except for at least a portion of the        total amount of any component that is required to initiate and        propagate an emulsion polymerization. Thus, the bioactive        cationic latex provided herein can be made by any variety of        batch or by a semi-continuous processes. For example, the at        least one bioactive component can be provided as a dispersion        and can be added to the composition during the emulsion        polymerization process.

In one aspect, the bioactive latices of this invention can be providedor used as coatings, which can be applicable to medical implants,including artificial ball and socket joints, rods, stents, dentalimplants, pins, screws, catheters, and the like. Such coatings can alsobe provided on everyday surfaces, such as air-conditioning coils, airfilters, pipes, roofing, bathroom items, kitchen items, and the like.Such a coating can prevent microbial infections, such as bacteria andmold, in vehicles as well as homes, hospitals, and other buildings.Further examples of uses of the resultant products are use as an aqueoussolution or directly in powder form, for example, for sterilizingcooling-water circuits, or indirect use, for example by addition topaints or other surface coatings.

These and other features, aspects, embodiments, and advantages of thepresent invention will become apparent after a review of the followingdetailed description of the invention. It should be understood, however,that these aspects, embodiments, and examples are provided forillustrative purposes only, and are not to be construed in any way asimposing limitations upon the scope thereof.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides new latex polymeric materials that can beused in combination with a wide variety of substrates, such as textiles,metal, cellulosic materials, plastics, and the like, in which thepolymeric materials include bioactive components incorporated into thelatex polymer. This invention also provides new methods and processesthat allow incorporating high concentrations of an active ingredientsuch as antifungal agents during the emulsion polymerization. In oneaspect, for example, the disclosed process can be used to incorporatefrom about 0.01 percent to about 40 percent, based on the total monomerweight (“phm” or parts per hundred of monomer), of a substantiallyhydrophobic bioactive ingredient during the emulsion polymerization.While the bioactive ingredient can be introduced at any stage during thepolymerization process including very early during the seed formationstage, in one aspect, the bioactive component or additive (bioadditive)can be added during the later stages of polymerization process, forexample, when from about 30 percent to about 90 percent of the monomerhas been fed into the polymerization reactor.

Useful bioactive additives can be solids, liquids, or combinationsthereof. Many of the bioactive additives that can be employed in thisinvention are substantially water insoluble or have limited solubilityin water. In this aspect, the typical water insoluble, hydrophobicbioactive agent can be soluble in at least one of the monomers employedin the emulsion polymerization. Thus, the typical hydrophobic bioactiveingredient can be introduced into the polymerization reactor bysubstantially or partially dissolving it in a monomer feed at theappropriate time. Therefore, the typical ingredients chosen forimparting antimicrobial properties usually will be soluble in themonomers that are used to make the polymer latex. In another aspect,useful bioactive additives in this invention can also be substantiallywater soluble, examples of which include o-phenylphenate (deprotonatedo-phenylphenol), and similar agents. In this aspect, it is not necessarythat such a hydrophilic bioactive additive be soluble in any monomerthat is to be polymerized.

In another aspect, it is not required that antimicrobial ingredients besoluble in at least one of the monomers used, as these ingredients canalso be added as a pre-made dispersion in water. In this aspect, thedispersions can be made, among other ways, by using a relativelyconcentrated amount of the additive and dispersing by using surfactants,dispersants, and the like, and typically employing a mixing device suchas a high speed mixer, a homogenizer, an Eppenbach mixer, or similardevices. In such a case, the dispersion can be fed into the reactor todeliver the appropriate amount of active ingredient into the latex.

In one aspect, this invention encompasses a bioactive cationic polymerlatex comprising:

-   -   a) a latex polymer comprising the polymerization product of: i)        at least one ethylenically unsaturated first monomer; and ii) at        least one ethylenically unsaturated second monomer that is        cationic or a precursor to a cation;    -   b) at least one bioactive component at least partially        encapsulated within the latex polymer; and    -   c) optionally, at least one sterically bulky component        incorporated into the latex polymer.        As provided herein, the at least one sterically bulky component        incorporated into the latex polymer can be selected        independently from at least one sterically bulky ethylenically        unsaturated third monomer, at least one sterically bulky        polymer, or any combination thereof. Each of these components,        as well as optional or additional components, is considered        herein.

In another aspect, this invention also encompasses a method of making abioactive cationic polymer latex comprising initiating an emulsionpolymerization of an aqueous composition comprising, at any time duringthe emulsion polymerization:

-   -   a) at least one ethylenically unsaturated first monomer;    -   b) at least one ethylenically unsaturated second monomer that is        cationic or a precursor to a cation;    -   c) at least one bioactive component;    -   d) at least one free-radical initiator;    -   e) optionally, at least one sterically bulky ethylenically        unsaturated third monomer;    -   f) optionally, at least one sterically bulky polymer; and    -   g) optionally, at least one non nonionic surfactant.

In yet another aspect, this invention provides a method of making abioactive cationic polymer latex comprising

-   -   a) providing an aqueous composition comprising:        -   i) at least one ethylenically unsaturated first monomer;        -   ii) at least one ethylenically unsaturated second monomer            that is cationic or a precursor to a cation;        -   iii) optionally, at least one sterically bulky ethylenically            unsaturated third monomer;        -   iv) at least one free-radical initiator; and        -   v) optionally, at least one non-ionic surfactant;    -   b) initiating an emulsion polymerization of the composition; and    -   c) adding at least one bioactive component to the composition        during the emulsion polymerization process.

Many compounds and species that can be used as ethylenically unsaturatedfirst monomers, ethylenically unsaturated second monomers, andsterically bulky components are disclosed in the European Patent NumberEP 1109845 and the corresponding PCT Published Patent Application WO00/8008077, each disclosure of which is incorporated herein by referencein its entirety.

Ethylenically Unsaturated First Monomers

Various ethylenically unsaturated first monomers can be used in thelatex of the present invention. In one aspect, ethylenically unsaturatedfirst monomers can be non-cationic. Examples of suitable monomers can befound at least in U.S. Pat. No. 5,830,934, U.S. Patent ApplicationPublication Nos. 2005/0065284 and 2005/0003163, and European PatentNumber EP 1109845, all to Krishnan, each disclosure of which isincorporated herein by reference in its entirety. In this aspect,examples of such monomers include, but are not limited to, vinylaromatic monomers, halogenated or non-halogenated olefin monomers,aliphatic conjugated diene monomers, non-aromatic unsaturated mono- ordicarboxylic ester monomers, monomers based on the half ester of anunsaturated dicarboxylic acid monomers, unsaturated mono- ordicarboxylic acid monomers, nitrogen-containing monomers,nitrile-containing monomers, cyclic or acyclic amine-containing monomer,branched or unbranched alkyl vinyl ester monomers, halogenated ornon-halogenated alkyl acrylate monomers, halogenated or non-halogenatedaryl acrylate monomers, carboxylic acid vinyl esters, acetic acidalkenyl esters, carboxylic acid alkenyl esters, a vinyl halide, avinylidene halide, or any combination thereof, any of which having up to20 carbon atoms. In this aspect, it is the Applicant's intent todisclose acrylate and methacrylate moieties when either moiety isdisclosed in a suitable monomer. Thus, the disclosure that an acrylatemonomer is a suitable ethylenically unsaturated first monomer alsoencompasses the disclosure that the corresponding methacrylate monomeris also a suitable first monomer. The abbreviation (meth)acrylate can beused to represent such a disclosure.

Many different ethylenically unsaturated first monomers can be used inpreparing the bioactive latices of this invention. In one aspect,suitable examples of ethylenically unsaturated first monomers include,but are not limited to, styrene, para-methyl styrene, chloromethylstyrene, vinyl toluene, ethylene, butadiene, methyl (meth)acrylate,ethyl(meth)acrylate, propyl(meth)acrylate, butyl(meth)acrylate,pentyl(meth)acrylate, glycidyl(meth)acrylate, isodecyl(meth)acrylate,lauryl (meth)acrylate, monomethyl maleate, itaconic acid,(meth)acrylonitrile, (meth)acrylamide, N-methylol (meth)acrylamide,N-(isobutoxymethyl)(meth)acrylamide, vinyl neodecanoate, vinylversatates, vinyl acetate, C₃-C₈ alkyl vinylethers, C₃-C₈ alkoxy vinylethers, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidenefluoride, trifluoroethylene, tetrafluoroethylene,chlorotrifluoroethylene, hexafluoropropylene, chlorotrifluoroethylene,perfluorobutyl ethylene, perfluorinated C₃-C₈ alpha-olefins, fluorinatedC₃-C₈ alkyl vinylethers, perfluorinated C₃-C₈ alkyl vinylethers,perfluorinated C₃-C₈ alkoxy vinyl ethers, and the like, or anycombination thereof. Thus, halogenated analogs of suitable ethylenicallyunsaturated first monomers are encompassed by this disclosure, and it isApplicant's intent to disclose any and all suitable halogen-substitutedanalogs or derivatives of these monomers, including fluorine-substitutedanalogs, chlorine-substituted analogs, bromine-substituted analogs, andiodine-substituted analogs. The term “halogen-substituted” is meant toinclude partially halogen substituted and perhalogen substituted, inwhich any halogen substituents can be the same or can be different. Inthis aspect as well, it is the Applicant's intent to disclose bothacrylate and methacrylate moieties when either moiety is disclosed in asuitable monomer.

In another aspect, the ethylenically unsaturated first monomer can behalogenated or can be non-halogenated. Similarly, the ethylenicallyunsaturated first monomer can be fluorinated or can be non-fluorinated.For example, fluorinated analogs of alkyl acrylates or methacrylates canbe used, as well as the non-fluorinated compounds. The ethylenicallyunsaturated first monomer can also be chlorinated or can benon-chlorinated. The ethylenically unsaturated first monomer can also bebrominated or can be non-brominated. The ethylenically unsaturated firstmonomer can also be iodinated or can be non-iodinated. For example,fluorinated analogs of alkyl acrylates or methacrylates can be used, aswell as the non-fluorinated compounds.

In yet another aspect of this invention, the latices provided herein cancomprise from about 20 percent to about 99.5 percent by weight of theethylenically unsaturated first monomer, based on the total monomerweight. In this aspect, the latex of this invention can also comprisefrom about 30 percent to about 99 percent, from about 40 percent toabout 97 percent, from about 50 percent to about 95 percent, from about60 percent to about 90 percent, or from about 70 percent to about 90percent by weight of the ethylenically unsaturated first monomer, basedon the total monomer weight. In this aspect, the Applicant's intent isto disclose individually each possible number that such ranges couldreasonably encompass, as well as any sub-ranges and combinations ofsub-ranges encompassed therein. In this aspect, as understood by theskilled artisan, the particular chemical and physical properties of aspecific monomer will have a bearing on the range of weight percentagesmost suitable for that monomer.

Ethylenically Unsaturated Cationic Second Monomers

In still another aspect, the latex polymer of the present invention alsocomprises the polymerization product of at least one ethylenicallyunsaturated second monomer that is cationic or a precursor to a cation.As provided herein, the at least one ethylenically unsaturated secondmonomer that is cationic or a precursor to a cation can be collectivelyreferred to by the term “cationic monomer,” that is, any monomer whichpossesses or can be made to posses a positive charge. In one aspect,this positive charge may be imparted by the presence of a heteroatom inthe monomer, such as nitrogen, that can constitute the site ofattachment of a proton or any other cationic Lewis Acid that wouldimpart a positive charge to the monomer. For example, quaternary aminemonomers can be used as a “cationic monomer” in the latex of theinvention, which includes quaternary amine monomers obtained from anyneutral amine monomer disclosed herein by, for example, protonationusing an acid or by alkylation using an alkyl halide. Exemplaryheteroatoms include, but are not limited to, nitrogen, sulfur,phosphorus, and the like. Thus, the cationic monomer is typicallyincorporated into the latex polymer by virtue of its ethylenicunsaturation.

Examples of suitable cationic monomers can be found at least in U.S.Patent Application Publication Nos. 2005/0065284 and 2005/0003163, toKrishnan. In this aspect, examples of cationic monomers include, but arenot limited to, an amine monomer, an amide monomer, a quaternary aminemonomer, a phosphonium monomer, a sulfonium monomer, or any combinationthereof, any of which having up to 20 carbon atoms. Further, suitableexamples of ethylenically unsaturated cationic monomers that can be usedin the latex of the present invention include, but are not limited to,dimethylaminoethyl acrylate; diethylaminoethyl acrylate; dimethylaminoethyl methacrylate; diethylaminoethyl methacrylate; tertiarybutylaminoethyl methacrylate; N,N-dimethyl acrylamide;N,N-dimethylaminopropyl acrylamide; acryloyl morpholine; N-isopropylacrylamide; N,N-diethyl acrylamide; dimethyl aminoethyl vinyl ether;2-methyl-1-vinyl imidazole; N,N-dimethyl-aminopropyl methacrylamide;vinyl pyridine; vinyl benzyl amine; dimethylaminoethyl acrylate, methylchloride quarternary; dimethylaminoethyl methacrylate, methyl chloridequarternary; diallyldimethylammonium chloride; N,N-dimethylaminopropylacrylamide, methyl chloride quaternary;trimethyl-(vinyloxyethyl)ammonium chloride;1-vinyl-2,3-dimethylimidazolinium chloride; vinyl benzyl aminehydrochloride; vinyl pyridinium hydrochloride; or any combinationthereof. While these listed examples include both free base compounds,and various quarternary salts such as hydrochloride or methyl chloridequarternary salts, any suitable Lewis acid that imparts a positivecharge to the monomer can be used to form the cationic monomers of thisdisclosure.

In a further aspect, other amines or amine salts can also be used asethylenically unsaturated second monomers to prepare the latex polymerof the present invention. For example, various amine salts can beobtained, for example, by the reaction of an epoxy group with asecondary amine and the subsequent neutralization of the newly formedtertiary amine with an acid. For example, the reaction of glycidylmethacrylate with a secondary amine can be carried out and the productcan be free radically polymerized. Quaternary amine functionality canalso be generated as a “post-reaction” on a preformed polymer having,for example, an epoxy group. Examples of such reactions are described inthe article, “Polymer Compositions for Cationic ElectrodepositableCoatings,” Journal of Coatings Technology, Vol 54, No 686, March 1982,which is incorporated herein by reference in its entirety. It shouldalso be appreciated that cationic functionality can also be impartedusing sulfonium or phosphonium chemistry, examples of which aredescribed in this reference, as will be appreciated by one of ordinaryskill in art.

In a further aspect, the latex polymer of this invention can comprisefrom about 0.01 to about 75 percent by weight of the ethylenicallyunsaturated second monomer that is cationic or a precursor to a cation,based on the total monomer weight. In this aspect, the latex of thisinvention can also comprise from about 0.025 to about 70 percent, fromabout 0.05 to about 60 percent, from about 0.1 to about 50 percent, fromabout 0.25 to about 40 percent, from about 0.5 to about 30 percent, fromabout 1 to about 20 percent, or from about 1.5 to about 15 percent, byweight of the cationic second monomer, based on the total monomerweight. In this aspect, the Applicant's intent is to discloseindividually each possible number that such ranges could reasonablyencompass, as well as any sub-ranges and combinations of sub-rangesencompassed therein.

Sterically Bulky Components

As disclosed herein, one aspect of this invention encompasses a cationicpolymer latex comprising: a) a latex polymer as disclosed herein; b) atleast one bioactive component at least partially encapsulated within thelatex polymer; and c) optionally, at least one sterically bulkycomponent incorporated into the latex polymer. The at least onesterically bulky component incorporated into the latex polymer can beselected independently from at least one sterically bulky ethylenicallyunsaturated third monomer, at least one sterically bulky polymer, or anycombination thereof. In this aspect, and while not intending to be boundby theory, this sterically bulky component is typically incorporatedinto the cationic polymer latex to sterically stabilize the latex.

As used herein, the term “incorporated” with respect to the use of theat least one sterically bulky ethylenically unsaturated third monomerincludes, but is not limited to, the attachment of this third monomer tothe cationic polymer, for example, by co-polymerization of the thirdmonomer with the first monomer and second cationic monomer disclosedherein, to form the cationic polymer latex. Further, the term“incorporated” with respect to the at least one sterically bulkyethylenically unsaturated third monomer can also include the attachmentof this third monomer to the cationic polymer in any other fashion, suchas, for example, by grafting onto the polymer backbone. In anotheraspect, the term “incorporated” with respect to the use of the at leastone sterically bulky polymer includes, but is not limited to, theattachment or association of this polymer into the latex for methodsincluding, but not limited to, adsorbing or grafting the stericallybulky polymer onto the latex surface. For example, polyvinyl alcohol canbe incorporated into the latex in this manner. This stericallystabilizing component can encompass a nonionic monomer or nonionicpolymer which incorporate steric stabilization to the latex particlewithout affecting the deposition characteristics of the cationic polymerlatex.

Exemplary monomers that can be used as sterically bulky ethylenicallyunsaturated third monomers include, but are not limited to, thoseethylenically unsaturated monomers that contain alkoxylated (forexample, ethoxylated or propoxylated) functionalities. In one aspect,examples of such monomers include, but are not limited to, at least onea sterically bulky ethylenically unsaturated compound selectedindependently from the following:

a) CH₂═C(R^(1A))COO(CH₂CHR^(2A)O)_(m)R^(3A), wherein R^(1A), R^(2A), andR^(3A) can be selected independently from H or an alkyl group havingfrom 1 to 6 carbon atoms, inclusive, and m can be an integer from 1 to30, inclusive. In this aspect, R^(1A), R^(2A), and R^(3A) can also beselected independently from H or methyl, m can be an integer from 1 to10, inclusive;

b) CH₂═C(R^(1B))COO(CH₂CH₂O)_(n)(CH₂CHR^(2B)O)_(p)R^(3B), whereinR^(1B), R^(2B), and R^(3B) can be selected independently from H or analkyl group having from 1 to 6 carbon atoms, inclusive, and n and p canbe integers selected independently from 1 to 15, inclusive. Also in thisaspect, R^(1B), R^(2B), and R^(3B) can be selected independently from Hor methyl, and n and p can be integers selected independently from 1 to10, inclusive;

c) CH₂═C(R^(1C))COO(CH₂CHR^(2C)O)_(q)(CH₂CH₂O)_(r)R^(3C), whereinR^(1C), R^(2C), and R^(3C) can be selected independently from H or analkyl group having from 1 to 6 carbon atoms, inclusive, and q and r canbe integers selected independently from 1 to 15, inclusive. Further tothis aspect, R^(1C), R^(2C), and R^(3C) can be selected independentlyfrom H or methyl, and q and r can be integers selected independentlyfrom 1 to 10, inclusive; or

d) any combination of any of these compounds.

In another aspect of this invention, a number of other types ofunsaturated compounds can be used as sterically bulky ethylenicallyunsaturated third monomers include, but are not limited to,polymerizable surfactants. Thus, further examples of suitable stericallybulky ethylenically unsaturated third monomers include, but are notlimited to, alkoxylated monoesters of a dicarboxylic acid; alkoxylateddiesters of a dicarboxylic acid; polyoxyethylene alkylphenyl ethers suchas NOIGEN RN™; or any combination thereof. In this aspect, for example,ethoxylated mono- and diesters of diacids such as maleic and itaconicacids can also be used to achieve the desired stabilizing effect.Acrylate, methacrylate, vinyl and allyl analogs of surfactants, referredto as polymerizable surfactants, can also be used in this manner.Examples of such polymerizable surfactants include, but are not limitedto, TREM LF-40™ sold by Cognis. In one aspect, these surfactants aretypical in that they possess ethylenic unsaturation that allows thesurfactants to be incorporated into the latex polymer itself, as well aspossessing hydrophobic and hydrophilic functionality that varies. Inanother aspect, surfactants that are particularly applicable to thepresent invention include the nonionic surfactants, wherein thehydrophilic character is believed to be attributable to the presence ofalkylene oxide groups. Examples of suitable nonionic surfactantsinclude, but are not limited to, ethylene oxide, propylene oxide,butylene oxide, and the like. In such species, the degree ofhydrophilicity can vary based on the selection of functionality.

The at least one sterically bulky component incorporated into the latexpolymer can also constitute at least one polymer. Again, while notintending to be bound by theory, it is thought that such polymersprovide steric stability to the resulting latex polymer. Such polymersare sometimes referred to in the art as protective colloids. Examples ofsterically bulky polymers include, but are not limited to, polyvinylalcohols, polyvinyl pyrollidone, hydroxyethyl cellulose, and the like,including any combination of these materials. Moreover, mixtures orcombinations of any of the aforementioned sterically bulky monomers andany of these sterically bulky polymers can also be used as the at leastone sterically bulky component that is incorporated into the latexpolymer. A number of other monomers and polymers that can be used in thepresent invention that can impart stability are provided in U.S. Pat.No. 5,830,934 to Krishnan et al., the entirety of which is incorporatedherein by reference.

The optional at least one sterically bulky component can be present inan amount ranging from 0 to about 25 percent by weight, based on thetotal weight of the monomers. In this aspect, the latex of thisinvention can also comprise from about 0.1 to about 20 percent, fromabout 0.2 to about 18 percent, from about 0.5 to about 15 percent, fromabout 0.7 to about 12 percent, or from about 1 to about 10 percent byweight of the sterically bulky component, based on the total monomerweight. In this aspect, the Applicant's intent is to discloseindividually each possible number that such ranges could reasonablyencompass, as well as any sub-ranges and combinations of sub-rangesencompassed therein.

Free Radical Initiators

In still a further aspect, the latex of the present invention caninclude a free radical initiator, the selection of which is known to oneof ordinary skill in the art. Thus, while any polymerization initiatorwhether it is cationic or anionic in nature can be used as apolymerization initiator, for example, persulfates, peroxides, and thelike, typical initiators are azo-based compounds and compositions.Moreover, in this aspect, for producing a cationic latex, any freeradical initiator which generates a cationic species upon decompositionand contributes to the cationic charge of the latex can be utilized.Examples of such an initiator include, but are not limited to, is2,2′-azobis(2-amidinopropane)dihydrochloride), which is soldcommercially as WAKO V-50™ by Wako Chemicals of Richmond, Va.

Bioactive/Antimicrobial Agents and their Incorporation

The cationic latex polymerization and encapsulation method disclosedherein can be utilized with a wide range of antimicrobial agents.Cationic latex has proved very useful due, in part, to the inherentantimicrobial attributes of the cationic polymer which can besupplemented with at least one antimicrobial agent. In this aspect, thisinvention also provides methods to prepare an antifungal fortifiedcationic latex and to deposit such a latex through a wet end processonto pulp fibers, such that the resultant sheet of paper issubstantially antifungal. This method, which includes deposition ontopulp fibers, highlights the utility of this process that incorporates anantimicrobial active ingredient into a resulting cationic latex fordeposition, in part, because the process is facilitated by oppositecharges on the pulp fibers and the cationic latex. This opposite chargefeatures typically leads to substantial uniformity of deposition of thecationic latex on the fiber and a substantially homogeneous product. Inthis aspect, the typical initiators also include azo-based compounds andcompositions.

As provided herein, a wide range of polymerization conditions can beused. In one aspect, the bioactive component or additive is typicallysoluble in at least one of the monomers employed, and/or soluble in amonomer mixture or composition used. In another aspect, the bioactiveadditive can be introduced at any stage during the polymerizationprocess including very early during the seed formation stage, includinginitiating the emulsion polymerization when all the components of thecomposition, including the at least one bioactive component, are presentat the time of initiation. In another aspect, the bioadditive can beadded during a later stage of polymerization process. For example, thebioactive ingredient can be introduced into the monomer feed when about30 percent of the monomer has been fed into the polymerization reactor.

While not intending to be bound by theory, it is believed thatintroducing the bioactive component into the monomer feed relativelylate in the polymerization process could help minimize degradation ofthe bioactive agent arising from the polymerization conditions. Forexample, it is possible that the bioactive agent could be degraded atthe temperature under which polymerization is conducted, or could reactwith certain monomers or other components. Accordingly, to minimize anysuch degradation process, the bioactive agent can be added at such atime in the process, for example, when the process is more than about50%, more than about 60%, more than about 70%, more than about 80%, ormore than about 90% complete, thus minimizing the contact time betweenthe bioactive agent and other components under the polymerizationconditions. Another approach to minimize degradation of the bioactiveagent is to employ bioactive agents that comprise “latent” bioactivemoieties that can be activated by thermal, chemical, photochemical, orsimilar means, at a suitable time after the emulsion polymerization.

In another aspect of this invention, the bioactive additive can beintroduced at any stage during an emulsion polymerization process,including, for example at such a time during the process at which theresulting antimicrobial latex exhibits a bioactivity that is notsubstantially diminished relative to a standard bioactivity exhibited bythe same antimicrobial latex prepared by adding the bioactive componentwhen the emulsion polymerization is about 50% complete. Thus, thisstandard bioactivity is the activity of the same antimicrobial latexsynthesized from the same bioactive component and the same latex atsubstantially the same concentrations, prepared by adding the bioactivecomponent when the emulsion polymerization is about 50% complete, asevaluated under similar conditions. The term “not substantiallydiminished” is used to refer to any difference in activity of theresulting bioactive latex, relative to this standard bioactivity, thatmeets any one, or more than one, of the following criteria: 1) themeasured activity of the resulting bioactive latex is less than or equalto about 15% lower than the measured activity of the standard; 2) theactivity of the resulting bioactive latex has a numerical activityrating based on an arbitrary activity scale that is less than or equalto about 35% lower than the numerical activity rating of the standard;or 3) the empirically-based descriptive rating of the activity level ofthe resulting bioactive latex is no more than two descriptive ratinglevels lower than the activity rating level of the standard. Themeasurement of antimicrobial activity can be determined according to anyone, or more than one, of the following test standards: ASTM E2180-01;ASTM E2149-01; ASTM E1882-05; ASTM D3273; AATCC Test Method 30, Part 3;AATCC Test Method 100; ASTM D5590. An example of criterion 1) of “notsubstantially diminished” is as follows. A bioactive additive can beintroduced at a time, or introduction can be initiated at a time, duringan emulsion polymerization process so as to provide a resultingantimicrobial latex having a minimum inhibitory concentration (MIC) of0.009 mg/mL, which is less than 15% lower than a MIC of 0.010 mg/mL forthe standard. An example of criterion 2) of “not substantiallydiminished” is as follows. The bioactive additive can be introduced at atime, or introduction can be initiated at a time, during an emulsionpolymerization process so as to provide a resulting antimicrobial latexhaving numerical activity rating of bioactivity based on an arbitraryactivity scale of 5, which is less than 35% lower than the numericalactivity rating of bioactivity of 7 for the standard. An example ofcriterion 3) of “not substantially diminished” is as follows. In anempirically-based descriptive rating system that includes contiguousrating levels of “excellent activity,” “very good activity,” and “goodactivity,” the bioactive additive can be introduced at a time, orintroduction can be initiated at a time, during an emulsionpolymerization process so as to provide a resulting antimicrobial latexhaving an activity rating of “good activity,” as compared to an activityrating of “excellent activity” for the standard. In any of thesemeasurements of activity, the bioactive additive can be introduced atany time during the polymerization process that provides this result, orintroduction can be initiated at a time during the polymerizationprocess that provides the result disclosed above.

In another aspect, it is not necessary to introduce the bioactivecomponent into the monomer feed relatively late in the polymerizationprocess. For example, the bioadditive agent can also be added when about0 percent, about 10 percent, about 20 percent, about 30 percent, about40 percent, about 50 percent, about 60 percent, about 70 percent, about80 percent, about 90 percent, or about 100 percent of the monomer hasbeen fed into the polymerization reactor. In this aspect, the emulsionpolymerization is initiated at a time when all components of thecomposition are not present from the time of initiation, but some areadded at various times after initiating the polymerization, including,but not limited to, the at least one bioactive component. Also in thisaspect, the Applicant's intent is to disclose any and all ranges betweensuch numbers, and to claim individually each possible number that suchranges could reasonably encompass, as well as any sub-ranges andcombinations of sub-ranges encompassed therein.

In another aspect, polymerization can be effected at a range oftemperatures, typically selected between the lowest temperature thataffords reasonable polymerization rates, and the highest temperatureallowable that does not result in substantial degradation ordecomposition of the antimicrobial bioactive ingredient. In one aspect,the polymerization can be carried out at the lowest temperature possiblesuch that polymerization proceeds. In this case, the polymerizationtemperature should be sufficiently low to not substantially degrade ordecompose any bioactive ingredient that is incorporated, yet high enoughsuch that polymerization rates and times are adequate for usefulproduction of the final latex polymer.

The antimicrobial agent can also be fed as a pre-emulsion made byemulsifying a mixture of monomer, additive, surfactants, water, and thelike, using methods and materials known to one of ordinary skill in theart. For example, In this aspect, the dispersions can be made, amongother ways, by using a relatively concentrated amount of the additiveand dispersing by using surfactants, dispersants, and the like, andtypically employing a mixing device such as a high speed mixer, ahomogenizer, an Eppenbach mixer, or similar devices. Moreover, any otherconceivable process or process known to one of ordinary skill thatprovides emulsion polymers in which the additive is a dispersion, anemulsion, a suspension, or the like, or substantially dissolved in themonomer mixture prior to polymerization, can be utilized.

In one aspect, useful antimicrobial agents that provide antifungal andantibacterial properties can be, in many cases, susceptible to oxidationor reduction, especially when exposed to higher temperatures. Thereforein addition to antimicrobial agent solubility, another aspect ofselecting and incorporating antimicrobial agents is diminishing anyoxidation or reduction reaction that would degrade such components. Theprocesses of this invention can typically achieve this result bycontrolling the polymerization temperature, adjusting the time periodthat the active ingredient is added into the reaction to controlexposure to the polymerization temperature, by adding an appropriateoxidant or reductant at some time during the polymerization to diminishor moderate any redox degradation, or any combination of these methods.

In a further aspect of the present invention, the at least one bioactivecomponent can be selected independently from undecylenic acid;undecylenic alcohol; the reaction product of undecylenic acid withhydroxylethyl(meth)acrylate or polyethylene glycol (meth)acrylate; thereaction product of undecylenic alcohol with (meth)acrylic acid, maleicanhydride, or itaconic acid; chitosan or modified chitosans; or anycombination thereof. Additional antimicrobial components that can beused in the present invention are provided in U.S. Patent ApplicationPublication No. 2005/0003163, to Krishnan, which is incorporated hereinby reference in its entirety. Another aspect of this invention providesthat the at least one bioactive component can be selected independentlyfrom copper, copper salts, silver, silver salts, zinc, zinc salts,silver oxide, zinc oxide, chlorhexidine, chlorhexidine gluconate,glutaral, halazone, hexachlorophene, nitrofurazone, nitromersol,povidone-iodine, thimerosol, C₁- to C₅-parabens, hypochlorite salts,clofucarban, clorophene, poloxamer-iodine, phenolics, mafenide acetate,aminacrine hydrochloride, quaternary ammonium salts, oxychlorosene,metabromsalan, merbromin, dibromsalan, glyceryl laurate, pyrithionesalts, sodium pyrithione, zinc pyrithione,(dodecyl)(diethylenediamine)glycine, (dodecyl)(aminopropyl)glycine,phenol, m-cresol, o-cresol, p-cresol, o-phenyl-phenol, resorcinol, vinylphenol, polymeric guanidines, polymyxins, bacitracin, circulin,octapeptins, lysozmye, lysostaphin, cellulytic enzymes, vancomycin,ristocetin, actinoidins, avoparcins, tyrocidin A, gramicidin S, polyoxinD, tunicamycin, neomycin, streptomycin, or any combination thereof.

Yet another aspect of this invention provides that the at least onebioactive component can exhibit fungicidal activity. In this aspect,suitable fungicides that are applicable to this disclosure include, butare not limited to, azoles, quaternary ammonium compounds,dithiocarbamates, dicarboximides, or any combination thereof. Forexample, in this aspect, an azole fungicide can be selected fromazaconazole, biternatol, bromuconazole, cyproconazole, diniconazole,fenbuconazole, flusilazole, flutnafol, imazalil, imibenconazole,metconazole, paclobutrazol, perfuazoate, penconazole, simeconazole,triadimefon, triadimenol, uniconazole, or any combination thereof. Alsoin this aspect, a dithiocarbamate fungicide can be selected frommancozeb, maneb, metiram, zineb, or any combination thereof.

In another aspect, suitable fungicides can include, but are not limitedto, fludioxonil, fluquinconazole, difenoconazole,4,5-dimethyl-N-(2-propenyl)-2-(trimethylsilyl)-3-thiophenecarboxamide(sylthiopham), hexaconazole, etaconazole, triticonazole, flutriafol,epoxiconazole, bromuconazote, tetraconazole, myclobutanil, bitertanol,pyremethanil, cyprodinil, tridemorph, fenpropimorph, kresoxim-methyl,azoxystrobin, ZEN90160™, fenpiclonil, benalaxyl, furalaxyl, metalaxyl,R-metalaxyl, orfurace, oxadixyl, carboxin, prochloraz, triflumizole,pyrifenox, acibenzolar-S-methyl, chlorothalonil, cymoxanil,dimethomorph, famoxadone, quinoxyfen, fenpropidine, spiroxamine,triazoxide, BAS50001F™, hymexazole, pencycuron, fenamidone, guazatine,and the like, including any combination thereof. Still another aspect ofthis invention provides that suitable fungicides can include, but arenot limited to, benomyl (also known as benlate), captan, carbendazim,capropamid, ethirimol, flutolanil, fosetyl-aluminum, fuberidazole,hymexanol, kasugamycin, iminoctadine-triacetate, ipconazole, iprodione,mepronil, metalaxyl-M (mefenoxam), nuarimol, oxine-copper, oxolinicacid, perfurazoate, propamocarb hydrochloride, pyroquilon, quintozene(also known as PCNB), silthiopham, MON™ 65500, tecnazene, thiabendazole,thifluzamide, thiophenate-methyl, thiram, tolclofos-methyl,triflumizole, and the like, including any combination thereof. Moreoverany combination or mixture of any of these fungicides can be employed.

In yet another aspect of this invention, typical amounts of bioactivecomponent that can be added during the emulsion polymerization can rangefrom about 0.01 percent to about 40 percent by weight bioactiveadditive, based on the total monomer weight. In another aspect, typicalamounts of bioactive component that can be added during the emulsionpolymerization can range from about 0.025 percent to about 35 percent,from about 0.05 percent to about 30 percent, from about 0.1 percent toabout 25 percent, from about 0.25 percent to about 20 percent, or fromabout 0.5 percent to about 15 percent by weight bioactive additive,based on the total monomer weight. In this aspect, the Applicant'sintent is to disclose individually each possible number that such rangescould reasonably encompass, as well as any sub-ranges and combinationsof sub-ranges encompassed therein. As compared to the amount ofantimicrobial component added as a “post-add,” these concentrations ofbioactive additive are typically much larger than the post-add amounts.Among other things, this features provides stable, concentrateddispersions that can be used as concentrates, as additives, or asconcentrated dispersions that can be diluted and added to other systemswhich require antimicrobial protection.

As disclosed herein, in one aspect, the bioactive component is typicallydissolved in the monomer feed during the emulsion polymerizationprocess. Thus, the bioactive additive is typically at least partiallysoluble in one or more of the monomers employed. Further, the bioactiveadditive can be moderately soluble, substantially soluble, or highlysoluble in one or more of the monomers employed. This feature can allow,among other things, the incorporation of hydrophobic bioactiveingredients, the use of high amounts and concentrations of bioactiveingredients, greater control over the antimicrobial properties includingenhancing the effectiveness of the antimicrobial properties, the use ofminimal amounts of surfactant, and at least partial encapsulation of thebioactive ingredient. In some instances, the latex polymer cansubstantially encapsulate the added bioactive component, thus the latexpolymer can function as a type of carrier for the active ingredients.This process also allows for the incorporation of the antimicrobialingredients without substantially degrading the activity of thesecompounds.

In another aspect, useful bioactive additives in this invention can alsobe water soluble to any extent, including substantially water soluble,examples of which include o-phenylphenate (deprotonated o-phenylphenol),and similar agents. Thus, it is not necessary that such a hydrophilicbioactive additive be soluble in any monomer that is to be polymerized.In still another aspect, useful bioactive additives in this inventioncan be substantially insoluble in the monomers being polymerized andsubstantially insoluble in water. In this aspect, a dispersion of thebioactive component can be made by, among other ways, by dispersing acertain concentration of the additive with the use of surfactants andthe like, typically with the use of high speed mixers or homogenizers.

Because the post-added additives are typically dispersions that arepost-mixed into a formulation, it can be difficult to adequatelydisperse the bioactive additive into the polymer film, binder, coating,or the like, in which they are used. Moreover, typical additivedispersions that are used today can cause or be associated with moisturesensitivity and leaching of the additive, and many post-adds do notpersist within the product for a sufficient period of time to provideadequate antifungal protection. The approach provided in this disclosureallows the use of minimal surfactants to incorporate the bioactiveadditives into the latex, and because the bioactives are introducedduring the polymerization, they are typically encapsulated and are noteasily released from the resulting latex. As a result, there can be lessleaching of the bioactive component, and better overall distribution ofthe bioactive ingredient throughout the polymer film, binder, coating,and the like. Accordingly, this method can provide a potentially saferand more environmentally friendly dispersion, while also offeringsustained antifungal or antibacterial protection.

The process disclosed herein also allows the latex to be used as aconcentrate, in contrast to the typical concentrate dispersions that arenot as stable as those provided herein. As a result, the typicalconcentrate dispersions are not as easily manipulated and thereforecannot be incorporated as easily into a finished product, and can havedeleterious effects on performance, such as water sensitivity, if dosageis increased. A concentrate of the latex provided herein can be dilutedand used with or without other materials if such materials are needed toprovide an adequate level of additive. Intimate incorporation of anactive ingredient in this manner can afford a homogeneous distributionof the additive and result in superior and sustained performancecompared to a pre-made dispersions. An additional benefit of thisintimate incorporation of the bioactive agent is apparent in films thatare prepared using these latices, which are observed to be substantiallytransparent. This feature highlights the highly homogeneous assimilationof the bioactive agent into the latex particles and how this uniformdistribution can provide useful properties for applications such astransparent bioactive films and the like.

Other Additives

In another aspect of this disclosure, the latex provided herein can alsoinclude other additives to improve the physical and/or mechanicalproperties of the polymer, the selection of which are known to oneskilled in the art. Such additives include, for example, processing aidsand performance aids, including but are not limited to, cross-linkingagents, natural or synthetic binders, plasticizers, softeners,foam-inhibiting agents, froth aids, flame retardants, dispersing agents,pH-adjusting components, sequestering or chelating agents, or otherfunctional components, or any suitable combination thereof.

Exemplary Substrates and Applications for Bioactive Cationic PolymerLatices

The deposition of the latex polymer coatings of this disclosure on anynumber of different substrates, such as textiles, metal, cellulosicmaterials, plastics, and the like, can impart desired end-useperformance properties to those materials, and therefore tailor thesubstrates for a range of applications. For example, in one aspect, thepresent disclosure provides a treated fibrous material which cancomprise at least one fiber and at least one bioactive cationic polymerlatex as provided herein. In one aspect, the treated fibrous materialcan comprise at least one fiber and at least one bioactive cationicpolymer latex deposited on, or associated with, the at least one fiber.If desired, the bioactive cationic polymer can be applied to the fiberin the form of a powder, or the polymer composition can be deposited onthe fiber by any suitable method known to the skilled artisan.

As used herein, the term “fiber” is intended to be broadly construed andcan include single or multiple filaments that can be present in avariety of ways. It should be appreciated that only a single fiber canbe treated with the bioactive cationic polymer latex of the invention ifso desired. Fibers that can be used in conjunction with this inventioncan encompass natural fibers, synthetic fibers, or any combination ormixture thereof. Natural fibers include, but are not limited to, animalfibers (for example, silk and wool); mineral fibers (for example,asbestos); and vegetable-based fibers (for example, cotton, flax, jute,and ramie). Synthetic fibers include, but are not limited to, those madefrom polymers such as polyamides, polyesters, acrylics, and polyolefins.Other examples of fibers include, but are not limited to, rayon andinorganic substances extruded in fibrous form such as glass, boron,boron carbide, boron nitride, carbon, graphite, aluminum silicate, fusedsilica, and metals such as steel. In another aspect, cellulosic or woodfibers also can be treated with the bioactive cationic polymer latex ofthe invention if so desired. Recycled fibers using any suitable fibersuch as the above materials may also be employed. Any mixture of fiberscan be treated with the bioactive cationic polymer latex of theinvention if so desired.

The treated fibrous material can, in another aspect, have at least oneother polymeric layer deposited on the fiber so as to form a compositefibrous structure, thus multiple polymeric layers of various types canbe used if desired. For example, anionic polymer latices may bedeposited on the treated fibrous material to enhance specific propertiesof the treated fibrous material. In another aspect, the fibrous materialcan be treated in a sequential fashion using, alternately, bioactivecationic polymer latices and anionic polymer latices, to form multiplelayered structure. While not intending to be bound by theory, it isthought that simple coulombic interactions between cationic and anionicpolymers enhance the stability of such structures, leading to treatedfibrous materials that are robust. Layers of various other non-bioactivepolymers can be employed similarly, for example, deposited on thecationic polymer latex which is present on the fibrous material to forma composite structure. In this fashion, unique layering architecture canbe constructed with specially modified surfaces in accordance with thisinvention.

In a further aspect, the present invention also provides an article ofmanufacture comprising a substrate and a bioactive cationic polymerlatex deposited or positioned thereon, as provided herein. For thepurposes of this disclosure, the term “substrate” is intended to beconstrued and interpreted broadly to include all those formed frominorganic materials, organic materials, composites thereof, mixturesthereof, or any type of combination thereof. For example, the substratecan encompass, but is not limited to, fibers, fillers, pigments, and thelike, as well as other organic and inorganic materials.

In one aspect of this invention, as disclosed herein, a fibroussubstrate can be employed. The term “fibrous substrate” is also intendedto be construed and interpreted broadly to include at least all thefibers, woven textiles, and non-woven textiles disclosed herein. Thus,the fibrous substrate may be present, for example, in the form of a web,a yarn, a fabric, a textile substrate, and the like. Further examples offibrous substrates include, but are not limited to, natural fibers suchas cotton and wool to synthetic fibers such as nylon, acrylics,polyesters, urethanes, and the like. Known application processes can beused to apply the bioactive cationic polymer latex, such as rod/knifecoating, impregnation, back coatings, printing, as pretreatments onindividual fibers, or as a finished good. Also as used herein, the term“textile substrate” can be defined according to its use in U.S. Pat. No.5,403,640 to Krishnan et al., the disclosure of which is incorporatedherein by reference in its entirety. In this aspect, for example,“textile substrate” can encompass a fiber, a web, a yarn, a thread, asliver, a woven fabric, a knitted fabric, a non-woven fabric, anupholstery fabric, a tufted carpet, a pile carpet, and the like,including any combination thereof, formed from any of the fibersdescribed herein.

The bioactive cationic latex composition of this invention also can beapplied to a wide variety of plastic or rubber substrates. Examples ofsuch materials include, but are not limited to, commodity moldedthermoplastics such as polyolefins; engineering thermoplastics such aspolysulfones, acetals, polycarbonates, and the like; thermosets such asepoxies, urethanes, and related materials; and as extruded or blownfilms. The polymer could be applied as a coating on the surface byrod/knife coating, spray, dipping, as a laminate coating during theextrusion process, or as a coating applied in the mold during themolding process. Rubber products could include sheets, extruded/moldedarticles, composites, and the like. In another aspect, the bioactivecationic latex compositions of this invention also can be deployed insolid form. In this aspect, for example, the inventive latices can becoagulated or spray-dried to provide the solid bioactive cationic latex,which can be employed in solid form as an additive in plastic products,in processes such as extrusion or blow molding, as additives for variouspolyethylenes, polypropylenes, and the like, and in any number of otherpolymer and plastic applications.

The bioactive cationic latex composition of this invention also can beapplied to wood or metal substrates. In this aspect, suitable substrateswould include all kinds of natural and engineered wood substrates.Suitable metal substrates would include both metals and metal alloys,such as carbon steel, stainless steel, and including solid steel bars,sheets, coils, ropes, and such, wherein the composition is applied as acoating by one of the numerous processes such as spraying dipping,brushing, roller coating, and related methods.

In this context, an article of manufacture comprising a substrate and abioactive cationic polymer latex deposited or positioned thereon can bemade in accordance with standard procedures known to one of ordinaryskill in the relevant art. The article of manufacture can have, inanother aspect, at least one other polymeric layer deposited thereon soas to form a composite structure, thus multiple polymeric layers ofvarious types can be used if desired. For example, other layers ofvarious polymers can be deposited on the bioactive cationic polymerlatex which is present in the article of manufacture to form a compositestructure. In this aspect, deposition of a bioactive cationic latex canbe followed by the deposition of an anionic latex or other polymers toenhance specific properties of the article of manufacture. Thus,uniquely tailored articles with specially modified surfaces can be madein accordance with the present invention.

In a broader aspect, the present invention also provides a coatedmaterial comprising any material and a bioactive cationic polymer latexdeposited or positioned thereon, wherein additional layers of othermaterials optionally can be used in combination with the bioactivecationic polymer latex of this invention. As used herein, the term“material” is intended to be used broadly to include, but not be limitedto, any inorganic material, any organic material, any composite thereof,or any combination thereof. Examples of suitable materials include, butare not limited to, a fiber, a filler, a particle, a pigment, compositesthereof, combinations thereof, mixtures thereof, and the like.

A multiple deposition process can also be used to make composite filmsthat have applications in areas other than textiles and fibrousmaterials. In one aspect, for example, a bioactive cationic polymerlatex of this invention can be used to fabricate multilayer elastomericgloves. Cellulosic structures can also be made using the bioactivecationic polymer latex provided herein including, but not limited to,cellulosic composites and heavy duty cellulosic structures. Examples ofcellulosic composites include, but are not limited to, those compositesrelating to filtration, shoe insoles, flooring felt, gasketing, and thelike. Heavy duty cellulosic structures include, but are not limited to,dunnage bags, industrial wipes, and related structures. In a furtheraspect, the deposition process and bioactive cationic polymer latex ofthis invention also can be used in other technology arts including, butnot limited to, flocculants, wet and dry strength additives forpapermaking, retention aids, cement modifications, dye fixation,redispersible powders, and the like.

The present invention can afford certain advantages as compared toprevious methods used to fabricate bioactive materials. In this aspect,for example, a bioactive cationic latex can be substantially depositedon a substrate such that residual bioactive latex does not remain in theprocessing fluid medium, providing a potential advantage from anenvironmental standpoint. Moreover, bioactive cationic latices can bepreferentially deposited on any substrate that carries a net negativecharge, and deposition can occur in a uniform manner, thereby using lesslatex polymer. Further to this aspect, and while not intending to bebound by theory, the bioactive cationic latex is thought to be capableof forming substantially uniform monolayers of polymer material on anegatively charged substrate, thereby allowing the use of less latex toprovide the desired coverage. Because the bioactive cationic latices canbe formed by existing emulsion polymerization processes, the fabricationmethods advantageously allow for the preparation of high molecularweight polymers.

The bioactive cationic polymer latices disclosed herein can also obviatethe need for cationic retention aids and cationic surfactants. In oneaspect, for example, the bioactive cationic polymer latices can besubstantially devoid of cationic surfactants. This feature can beparticularly desirable because cationic surfactants generally are notretained well and can cause foaming and other adverse effects in aquaticenvironments. However in another aspect, this disclosure also providesfor the use of bioactive agents that can exhibit cationic surfactantbehavior and/or for the use of retention aids. Moreover, if desired, thepolymer latices can be devoid of conventional surfactants including, forexample, nonionic surfactants.

As provided herein, the latex composition of the present invention canbe applied to a wide variety of substrates using various techniques thatare well known to one of ordinary skill in the art. As a result, thereare numerous applications for the present invention, many of which areprovided in the following listing. In this aspect, while this listing isnot comprehensive, specific applications include, but are not limitedto: textiles such as residential and commercial carpets or tiles; liquidand air filters for HVAC or vacuum cleaners, or automotive uses; medicalsurgical gowns, drapes, dressings, covers, and the like; pretreatmentfor fibers, printed or dyed fabrics for apparel, furnishings, sheets,towels, and the like; diapers and incontinence articles; interiorautomotive applications such as trim, upholstery, mats, filters, andsuch; upholstery coatings; laminating and bonding adhesives; foams forsound absorbency; foamed articles such as pillows and mattresses;belting or other machinery parts for food handling and the like; tapessuch as masking tapes, surgical tape, industrial tapes, and the like;electrical, industrial, and household cleaning wipes, cloths, andsponges; shoe products such as insoles, box toes, and such; plasticand/or rubber items such as tool handles, tool grips, toys, rubbergloves, sheets, or other articles; machinery housing such as forcomputers, display and diagnostic devices or instrumentation; medicaldevices such as catheters, balloons, tubing, syringes, diagnostic kits,and the like; packaging or product protection, as applied toperishables, computer peripherals, semiconductors, memory chips, CDs,DVDs, and the like; impact modifiers for acrylics, polycarbonates, andsuch; overdips or underdips for gloves such as gloves for clean rooms;breathable films; antipenetrant for fabric supported gloves; cuttingboards; extruded and blown films for packaging; paper products such asvacuum bags, book covers, air filters, liquid filters, wallcoverings,wet and dry wipes, tissues, and such; felt for vinyl floor coverings;molded pulp applications; packaging such as boxes, cartons, moldedarticles, and related items; size press coatings for gift wraps, ink jetmedia, breathable coatings, and the like; wet end additives in paper,tapes, labels for use in masking, surgical applications, general purposeapplications, and such; binders for use in paper; binders for use inwallboard such as gypsum wallboard and the like; adhesives for use intapes, labels, decals, films, book bindings, pressure sensitiveapplications, flexible packaging and laminating adhesive (FPLA), and thelike; inorganic and/or organic materials such as coating orencapsulation of fillers or pigments, construction sealers and grouts,gypsum wallboard coatings or binders, exterior or interior coatings, andthe like; tile adhesives; floor coatings for use in hospitals, cleanrooms, clinics, schools, and related environments; coatings for hospitaland medical environments; ceiling tiles; glass fiber coatings such asglass mats, insulation, filter materials, reinforced composites, andsuch; coatings for air conditioning or refrigeration coils; othercomponents for air conditioning systems, heat exchangers, ionexchangers, process water systems including cooling water treatment,solar-powered units, coated pipes, and the like; kitchen items;components of sanitary equipment; components of water systems; operatorunits of devices such as touch panels; materials used in bathrooms suchas shower curtains, fixtures, toilet items, and even jointing or sealingcompounds; medical devices such as use in coatings for stents, implants,prostheses, catheters, tubing, contact lenses, contact lens cleaners orstorage solutions, protective or backing films, medical instruments, andother medical devices for providing the sustained action of bioactiveagents; articles which are contacted by large numbers of people such astelephone handsets, stair rails, door handles, window catches, grabstraps and grab handles in public conveyances, and the like; wound orsurgical treatments; wound or surgical dressings, including any layerssuch as absorbent layers of wound or surgical dressings; medical orathletic tapes; surgical drapes; tapes or tabs used in adhering medicaldevices such as sensors, electrodes, ostomy appliances, or the like;liquid disinfectants and cleaners; personal care or hygiene productssuch as shampoos, lotions, creams, hair and skin care products, bodywash, cosmetics, toilet items, and the like; hygiene coatings ofsurfaces other than floors, such as in hospitals, clinics, schools,homes, offices, and the like; hard and porous surface coatings asapplicable to walls, ceilings, floors, counter tops, and the like;decorative concrete; wood such as oriented strand board (OSB) coatings;decking and construction materials for coating or impregnation;composite construction materials; furniture coatings; hygiene coatingssuch as used in table tops, counter tops, door knobs, door handles,fixtures, and the like; flooring applications such as in laminates,hardwood flooring, and other composite flooring materials; decorativelaminates such as table tops, counter tops, furniture, and the like;other construction materials such as roofing material, wall material,facades, fencing, or for wood protection applications; marineapplications such as in boat hulls, docks, buoys, drilling platforms, orballast water tanks; metal such as cabinets, door knobs, handles,fixtures, and such; and furniture, coatings as applicable to appliances,original equipment manufacture (OEM), and the like.

In this aspect, the antimicrobial formulations of the invention can beuseful as a biofouling inhibitor, in particular, in cooling circuits. Toprevent damage to cooling circuits by infestation with algae orbacteria, the circuits typically have to be cleaned frequently or beappropriately oversized. In the open cooling systems usually found inpower plants and in chemical plants, the addition of microbiocidalsubstances, such as formalin, is generally not possible. Othermicrobiocidal substances are frequently highly corrosive or form foams,preventing their use in systems of this type. Deposition of bacteria oralgae on components of the system can thus be effectively inhibited.Therefore, the formulations and materials of this invention can be quiteuseful in such applications.

In another aspect, the present invention can also provide a process forsterilizing cooling-water streams or process water systems, by addingantimicrobial formulations in dispersed form to the cooling water. Thedispersed form can be obtained in the preparation process itself, forexample, by emulsion polymerization as detailed herein, but also byprecipitation polymerization, or suspension polymerization, orsubsequently by milling of the antimicrobial polymer obtained by any ofthese methods, for example, in a jet mill.

The antimicrobial latex polymer of this invention can be applied or usedas a coating composition, which can be used for a wide variety ofpurposes in connection with which antimicrobial action is desired. Forexample, in one aspect, the antimicrobial latex polymers disclosedherein can be used in connection with a wide range of insulatingmaterials such as wrapping materials for pipes, which are a particularrisk of bacterial attack. Thus, the materials of the invention areuseful when used in connection with elastomeric insulating materials.Such coating compositions can also be used in connection with industrialinsulation, such as is used for insulating pipelines, examples beingheating pipes, and for insulating valves and ducts. Moreover,antimicrobial latices disclosed herein can be used in conjunction withall thermal and/or acoustic insulations and related insulating materialsfor numerous end applications. The latices provided herein can also beused in conjunction with industrial foams and foam materials assubstrates for antimicrobial coatings. Such coatings comprising theantimicrobial latices disclosed herein also can be used as coatings forair-conditioning plants, condensers, refrigerators and otherrefrigeration units, and also parts thereof, and also for coatingcompositions as paints for marine craft and for wood preservation.Coatings comprising the antimicrobial latices of this disclosure canalso be employed as the coating of substrates such as metal, plastic, orceramic, in hygiene installations, hospitals, or in the food industry,or any articles involving frequent contact of any type which may easilytransmit infection pathogens, such as door handles, sanitary fittings,switches, and grips. In the case of such coatings the use of a coatingcomposition in the form of powder coatings can be advantageous.

Applications of Antimicrobial Latices to Medical Devices The term“medical device” as used herein refers to any material, natural orartificial, that is inserted into a mammal, or used in the process ofinserting a material into a mammal. Particular medical devices suitedfor application of the antimicrobial latices and compositions of thisinvention include, but are not limited to, peripherally insertablecentral venous catheters, dialysis catheters, long term tunneled centralvenous catheters, long term non-tunneled central venous catheters,peripheral venous catheters, short-term central venous catheters,arterial catheters, pulmonary artery Swan-Ganz catheters, urinarycatheters, artificial urinary sphincters, long term urinary devices,urinary dilators, urinary stents, other urinary devices, tissue bondingurinary devices, penile prostheses, vascular grafts, vascular catheterports, vascular dilators, extravascular dilators, vascular stents,extravascular stents, wound drain tubes, hydrocephalus shunts,ventricular catheters, peritoneal catheters, pacemaker systems, small ortemporary joint replacements, heart valves, cardiac assist devices andthe like, bone prosthesis, joint prosthesis, dental prosthesis, and thelike.

In one aspect, the medical devices that can be used in conjunction withthe bioactive cationic latices of this invention include, but are notlimited to, non-metallic materials such as thermoplastic or polymericmaterials. Examples of such materials include rubber, plastic,polyethylene, polyurethane, silicone, GORTEX™ (polytetrafluoroethylene),DACRON™ (polyethylene tetraphthalate), polyvinyl chloride, TEFLON™(polytetrafluoroethylene), elastomers, nylon and DACRON™ sealed withgelatin, collagen or albumin. The amount of each bioactive cationiclatex used to coat the medical device varies to some extent, but is atleast a sufficient amount to form an effective concentration to inhibitthe growth of bacterial and fungal organisms.

The antimicrobial latices can be used alone or in combination of two ormore of them. Each antimicrobial latex can comprise one or moreantimicrobial components as provided herein. Any application or usedisclosed herein can further encompass the use of at least one bioactivelatex in conjunction with at least one other antimicrobial agent thatcan be dispersed throughout the surface of the medical device. Theamount of each bioactive latex and each antimicrobial agent used toimpregnate the medical device varies to some extent, but is at least ofan effective concentration to inhibit the growth of bacterial and fungalorganisms.

In one aspect, the antimicrobial agent can be selected from anantibiotic, an antiseptic, a disinfectant, or any combination thereof.In another aspect, the antimicrobial agent can be an antibioticincluding, but not limited to, penicillins, cephalosporins, carbepenems,other beta-lactam antibiotics, aminoglycosides, macrolides,lincosamides, glycopeptides, tetracylines, chloramphenicol, quinolones,fucidins, sulfonamides, trimethoprims, rifamycins, oxalines,streptogramins, lipopeptides, ketolides, polyenes, azoles,echinocandins, or any combination thereof.

In one aspect, at least one drug can be applied to a medical deviceusing bioactive latices provided herein, and used in combinations withdrugs that can adhere to, rather than be encapsulated by, the bioactivelatices. For example, a cationic antimicrobial latex coating can beapplied as a coating to a medical device that can have an ionic charge.Subsequently, drugs having a complimentary charge can be applied to, andcan bind to, the charged coating applied to the surface of device whenthe charged coating and the drug are exposed to one another. Thestrength of bonding between the drug and the coating can be used toinfluence how readily the drug can be released from the surface of thedevice. In one aspect, this disclosure provides for delivering animplant or medical device having this drug delivery feature to aselected anatomical site. In this aspect, typically drugs that areuseful include, but are not limited to, antimicrobials and antibioticssuch as neomycin and sulfa drugs, anti-inflammatory agents such assteroidal or non-steroidal anti-inflammatory agents, or combinationsthereof.

Although any methods, devices, and materials similar or equivalent tothose described herein can be used in the practice or testing of theinvention, the typical methods, devices and materials are hereindescribed. All publications and patents mentioned herein areincorporated herein by reference for the purpose of describing anddisclosing, for example, the constructs and methodologies that aredescribed in the publications, which might be used in connection withthe presently described invention. The publications discussed herein areprovided solely for their disclosure prior to the filing date of thepresent application. Nothing herein is to be construed as an admissionthat the inventors are not entitled to antedate such disclosure byvirtue of prior invention.

When Applicants disclose or claim a range of any type, for example arange of temperatures, a range of concentrations, a range of numbers ofatoms, a weight percent, or the like, Applicants' intent is to discloseor claim individually each possible number that such a range couldreasonably encompass, as well as any sub-ranges and combinations ofsub-ranges encompassed therein. Thus, when the Applicants disclose orclaim a chemical moiety having a certain number of carbon atoms,Applicants' intent is to disclose or claim individually every possiblenumber, sub-range, and combination of sub-ranges that such a numberrange could encompass, consistent with the disclosure herein. Forexample, the disclosure that R is selected from an alkyl group having upto 12 carbon atoms, or in alternative language a C₁ to C₁₂ alkyl group,as used herein, refers to an R group that can be selected from an alkylgroup having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms, aswell as any range between these two numbers for example a C₃ to C₈ alkylgroup, and also including any combination of ranges between these twonumbers for example a C₃ to C₅ and C₇ to C₁₀ alkyl group. Thus,Applicants retain the right to replace the terminology such as “grouphaving up to 12 carbon atoms” with any individual number that such arange could reasonably encompass, as well as any sub-ranges andcombinations of sub-ranges encompassed therein. In another example, bythe disclosure that the molar ratio typically spans the range from about0.1 to about 1.0, Applicants intend to recite that the molar ratio canbe selected from about 0.1:1, about 0.2:1, about 0.3:1, about 0.4:1,about 0.5:1, about 0.6:1, about 0.7:1, about 0.8:1, about 0.9:1, orabout 1.0:1, as well as any sub-ranges and combinations of sub-rangesencompassed therein. Similarly, the disclosure that a particular weightpercent can be from about 80 percent to about 90 percent by weight,Applicants' intend to recite that the weight percent can be about 80percent, about 81 percent, about 82 percent, about 83 percent, about 84percent, about 85 percent, about 86 percent, about 87 percent, about 88percent, about 89 percent, or about 90 percent, by weight.

Applicants reserve the right to proviso out or exclude any individualmembers of any such group, including any sub-ranges or combinations ofsub-ranges within the group, that may be claimed according to a range orin any similar manner, if for any reason Applicants choose to claim lessthan the full measure of the disclosure, for example, to account for areference that Applicants may be unaware of at the time of the filing ofthe application. Further, Applicants reserve the right to proviso out orexclude any individual substituents, additives, compounds, monomers,surfactants, structures, and the like, or any groups thereof, or anyindividual members of a claimed group, if for any reason Applicantschoose to claim less than the full measure of the disclosure, forexample, to account for a reference that Applicants may be unaware of atthe time of the filing of the application.

For any particular chemical compound disclosed herein, any generaldisclosure or structure presented also encompasses all isomers, such asconformational isomers, regioisomers, stereoisomers, and the like, thatcan arise from a particular set of substituents. The general structurealso encompasses all enantiomers, diastereomers, and other opticalisomers whether in enantiomeric or racemic forms, as well as mixtures ofstereoisomers, as the context requires.

The present invention is further illustrated by the following examples,which are not to be construed in any way as imposing limitations uponthe scope thereof. On the contrary, it is to be clearly understood thatresort can be had to various other aspects, embodiments, modifications,and equivalents thereof which, after reading the description herein, maysuggest themselves to one of ordinary skill in the art without departingfrom the spirit of the present invention or the scope of the appendedclaims.

In the following examples, unless otherwise specified, the reagents wereobtained from commercial sources. General procedures, including generalsynthetic testing procedures for cationic polymer latices, are providedin U.S. Patent Application Publication Nos. 2005/0065284 and2005/0003163, to Krishnan, each disclosure of which is incorporatedherein by reference in its entirety.

EXAMPLE 1

Bioactive Cationic Latex Prepared by Early Introduction of the BioactiveAgent

A one-gallon reactor can be charged with the following ingredients:about 1142 g of water; about 5.95 g of the nonionic surfactant ABEX™2525 (Rhodia); about 11.90 g of methoxy polyethyleneglycolmethacrylate(MPEG 550 from Cognis); and about 31.7 g of dimethylaminoethylmethacrylate methyl chloride quaternary (AGEFLEX™ FM1Q75MC from CibaSpecialty Chemicals). The reactor contents then can be deoxygenated bysubjecting the reactor to several vacuum/N₂ fill cycles, after whichabout 59.5 g of butyl acrylate and about 119 g of styrene can be addedto the reactor. The reactor is again subjecting to several vacuum/N₂fill cycles, after which the temperature of the reactor contents can beincreased to about 165° F., at which time an initiator solution of about23.80 g of water and about 2.38 g of WAKO V-50 (Wako Chemicals) isinjected into the reaction mixture. This reaction mixture is maintainedat about 165° F. for approximately 30 minutes before starting thefollowing feeds into the reactor.

After the 30 minute “hold period,” the following components can be fedinto the reactor:

1) A butadiene feed consisting of about 238 g of butadiene, fed overabout 5 hours;

2) A mixed monomer feed of about 102 g of butyl acrylate, about 517 g ofstyrene, and about 119 g of any suitable bioactive agent such as thosedisclosed herein. The total feed time of the entire mix can be about 5hours. The bioactive ingredient can be introduced into the mixed monomerfeed after about 1 hour of the mixed monomer feed, which involvesdissolving about 119 g of the bioactive agent in about 495 g of thestyrene/butyl acrylate monomer mixture that is introduced into thereactor over the final 4-hour feed period of the mixed monomer feed;

3) An aqueous monomer feed consisting of about 152 g of water, about47.60 g of MPEG 550 (Cognis), about 47.60 g of dimethylaminoethylmethacrylate methyl chloride quaternary (AGEFLEX™ FM1Q75MCfrom Ciba Specialty Chemicals), and about 74.5 g of N-methylolacrylamide. This aqueous monomer feed can be fed into the reactor overan approximately 3-hour period;

and

4) An aqueous initiator feed consisting of about 202 g of water andabout 4.8 g of WAKO™ V-50, which can be fed into the reactor over about5.5 hours;

When addition of the feeds is completed, the reaction is continued untilmost (greater than about 98%) of the monomers have reacted. The reactorcontents are then cooled down and the vacuum stripped to removeunreacted monomers and to raise the solids concentration to about 40percent by weight. If necessary or desired, the pH of the latex can beadjusted as required before stripping the reaction volatiles.

EXAMPLE 2

Bioactive Cationic Latex Prepared by Late Introduction of the BioactiveAgent

An emulsion polymerization reaction can be conducted according to thedetails provided in Example 2, except that an approximately 49 g-sampleof bioactive component can be introduced into the mixed monomer streamafter about 4 hours of a 5 hour styrene/butyl acrylate feed. Thisprocess involves dissolving the bioactive agent in about 124 g of thestyrene/butyl acrylate monomer mixture that is introduced into thereactor over the final 1-hour feed period of the mixed monomer feed.

In the specification, typical embodiments of the invention have beendisclosed and, although specific terms are employed, they are used in ageneric and descriptive sense and not for purposes of limitation. Thisinvention is further illustrated and described by the appended claims,however, it should be clearly understood that resort can be had tovarious other embodiments, aspects, modifications, and equivalents tothose disclosed in the claims, which, after reading the descriptionherein, may suggest themselves to one of ordinary skill in the artwithout departing from the spirit of the present invention or the scopeof these claims. The following claims are provided to ensure that thepresent application meets all statutory requirements as a priorityapplication in all jurisdictions and shall not be construed as settingforth the full scope of the present invention.

1. A bioactive cationic polymer latex comprising: a) a latex polymercomprising the polymerization product of: i) at least one ethylenicallyunsaturated first monomer; and ii) at least one ethylenicallyunsaturated second monomer that is cationic or a precursor to a cation;b) at least one bioactive component at least partially encapsulatedwithin the latex polymer; and c) optionally, at least one stericallybulky component incorporated into the latex polymer.
 2. The bioactivecationic polymer latex according to claim 1, wherein the at least oneethylenically unsaturated first monomer is selected independently from avinyl aromatic monomer, a halogenated or a non-halogenated olefinmonomer, an aliphatic conjugated diene monomer, a non-aromaticunsaturated mono- or dicarboxylic ester monomer, a monomer based on thehalf ester of an unsaturated dicarboxylic acid monomer, an unsaturatedmono- or dicarboxylic acid monomer, a nitrile-containing monomer, acyclic or an acyclic amine-containing monomer, a branched or anunbranched alkyl vinyl ester monomer, a halogenated or non-halogenatedalkyl acrylate monomer, a halogenated or non-halogenated aryl acrylatemonomer, a carboxylic acid vinyl ester, an acetic acid alkenyl ester, acarboxylic acid alkenyl ester, a vinyl halide, a vinylidene halide, orany combination thereof, any of which having up to 20 carbon atoms. 3.The bioactive cationic polymer latex according to claim 1, wherein theat least one ethylenically unsaturated first monomer is selectedindependently from styrene, para-methyl styrene, chloromethyl styrene,vinyl toluene, ethylene, butadiene, methyl (meth)acrylate,ethyl(meth)acrylate, propyl(meth)acrylate, butyl(meth)acrylate, pentyl(meth)acrylate, glycidyl(meth)acrylate, isodecyl(meth)acrylate,lauryl(meth)acrylate, monomethyl maleate, itaconic acid,(meth)acrylonitrile, (meth)acrylamide, N-methylol (meth)acrylamide,N-(isobutoxymethyl)(meth)acrylamide, vinyl neodecanoate, vinylversatates, vinyl acetate, a C₃-C₈ alkyl vinylether, a C₃-C₈ alkoxyvinylether, vinyl chloride, vinylidene chloride, vinyl fluoride,vinylidene fluoride, trifluoroethylene, tetrafluoroethylene,chlorotrifluoroethylene, hexafluoropropylene, chlorotrifluoroethylene,perfluorobutyl ethylene, a perfluorinated C₃-C₈ alpha-olefin, afluorinated C₃-C₈ alkyl vinylether, a perfluorinated C₃-C₈ alkylvinylether, a perfluorinated C₃-C₈ alkoxy vinyl ether, or anycombination thereof.
 4. The bioactive cationic polymer latex accordingto claim 1, wherein the at least one ethylenically unsaturated secondmonomer is selected independently from an amine monomer, an amidemonomer, a quaternary amine monomer, a phosphonium monomer, a sulfoniummonomer, or any combination thereof, any of which having up to 20 carbonatoms.
 5. The bioactive cationic polymer latex according to claim 1,wherein the at least one ethylenically unsaturated second monomer isselected independently from dimethylaminoethyl acrylate;diethylaminoethyl acrylate; dimethyl aminoethyl methacrylate;diethylaminoethyl methacrylate; tertiary butylaminoethyl methacrylate;N,N-dimethyl acrylamide; N,N-dimethylaminopropyl acrylamide; acryloylmorpholine; N-isopropyl acrylamide; N,N-diethyl acrylamide; dimethylaminoethyl vinyl ether; 2-methyl-1-vinyl imidazole;N,N-dimethyl-aminopropyl methacrylamide; vinyl pyridine; vinyl benzylamine; dimethylaminoethyl acrylate, methyl chloride quarternary;dimethylaminoethyl methacrylate, methyl chloride quarternary;diallyldimethylammonium chloride; N,N-dimethylaminopropyl acrylamide,methyl chloride quaternary; trimethyl-(vinyloxyethyl)ammonium chloride;1-vinyl-2,3-dimethylimidazolinium chloride; vinyl benzyl aminehydrochloride; vinyl pyridinium hydrochloride; or any combinationthereof.
 6. The bioactive cationic polymer latex according to claim 1,wherein the at least one sterically bulky component is selectedindependently from at least one sterically bulky ethylenicallyunsaturated third monomer, at least one sterically bulky polymer, or anycombination thereof.
 7. The bioactive cationic polymer latex accordingto claim 1, wherein the at least one sterically bulky component is atleast one a sterically bulky ethylenically unsaturated third monomerselected independently from: a)CH₂═C(R^(1A))COO(CH₂CHR^(2A)O)_(m)R^(3A), wherein R^(1A), R^(2A), andR^(3A) are selected independently from H or an alkyl group having from 1to 6 carbon atoms, inclusive, and m is an integer from 1 to 30,inclusive; b) CH₂═C(R^(1B))COO(CH₂CH₂O)_(n)(CH₂CHR^(2B)O)_(p)R^(3B),wherein R^(1B), R^(2B), and R^(3B) are selected independently from H oran alkyl group having from 1 to 6 carbon atoms, inclusive, and n and pare integers selected independently from 1 to 15, inclusive; c)CH₂═C(R^(1C))COO(CH₂CHR^(2C)O)_(q)(CH₂CH₂O)_(r)R^(3C), wherein R^(1C),R^(2C), and R^(3C) are selected independently from H or an alkyl grouphaving from 1 to 6 carbon atoms, inclusive, and q and r are integersselected independently from 1 to 15, inclusive; or d) any combinationthereof.
 8. The bioactive cationic polymer latex according to claim 1,wherein the at least one sterically bulky component is at least onesterically bulky ethylenically unsaturated third monomer selectedindependently from: a) CH₂═C(R^(1A))COO(CH₂CHR^(2A)O)_(m)R^(3A), whereinR^(1A), R^(2A), and R^(3A) are selected independently from H or methyl,and m is an integer from 1 to 10, inclusive; b)CH₂═C(R^(1B))COO(CH₂CH₂O)_(n)(CH₂CHR^(2B)O)_(p)R^(3B), wherein R^(1B),R^(2B), and R^(3B) are selected independently from H or methyl, and nand p are integers selected independently from 1 to 10, inclusive; c)CH₂═C(R^(1C))COO(CH₂CHR^(2C)O)_(q)(CH₂CH₂O)_(r)R^(3C), wherein R^(1C),R^(2C), and R^(3C) are selected independently from H or methyl, and qand r are integers selected independently from 1 to 10, inclusive; or d)any combination thereof.
 9. The bioactive cationic polymer latexaccording to claim 1, wherein the at least one sterically bulkycomponent is selected independently from: an alkoxylated monoester of adicarboxylic acid; an alkoxylated diester of a dicarboxylic acid; apolyoxyethylene alkylphenyl ether; a polymerizable surfactant; or anycombination thereof.
 10. The bioactive cationic polymer latex accordingto claim 1, wherein the at least one sterically bulky component is atleast one sterically bulky polymer selected independently from polyvinylalcohols, polyvinyl pyrollidone, hydroxyethyl cellulose, or anycombination thereof.
 11. The bioactive cationic polymer latex accordingto claim 1, wherein the at least one bioactive component is selectedindependently from undecylenic acid; undecylenic alcohol; the reactionproduct of undecylenic acid with hydroxylethyl (meth)acrylate orpolyethylene glycol (meth)acrylate; the reaction product of undecylenicalcohol with (meth)acrylic acid, maleic anhydride, or itaconic acid;chitosan or modified chitosans; or any combination thereof.
 12. Thebioactive cationic polymer latex according to claim 1, wherein the atleast one bioactive component is selected independently from copper,copper salts, silver, silver salts, zinc, zinc salts, silver oxide, zincoxide, chlorhexidine, chlorhexidine gluconate, glutaral, halazone,hexachlorophene, nitrofurazone, nitromersol, povidone-iodine,thimerosol, C₁- to C₅-parabens, hypochlorite salts, clofucarban,clorophene, poloxamer-iodine, phenolics, mafenide acetate, aminacrinehydrochloride, quaternary ammonium salts, oxychlorosene, metabromsalan,merbromin, dibromsalan, glyceryl laurate, pyrithione salts, sodiumpyrithione, zinc pyrithione, (dodecyl) (diethylenediamine)glycine,(dodecyl)(aminopropyl)glycine, phenol, m-cresol, o-cresol, p-cresol,o-phenyl-phenol, resorcinol, vinyl phenol, polymeric guanidines,polymyxins, bacitracin, circulin, octapeptins, lysozmye, lysostaphin,cellulytic enzymes, vancomycin, ristocetin, actinoidins, avoparcins,tyrocidin A, gramicidin S, polyoxin D, tunicamycin, neomycin,streptomycin, or any combination thereof.
 13. The bioactive cationicpolymer latex according to claim 1, wherein the at least one bioactivecomponent is selected independently from azaconazole, biternatol,bromuconazole, cyproconazole, diniconazole, fenbuconazole, flusilazole,flutnafol, imazalil, imibenconazole, metconazole, paclobutrazol,perfuazoate, penconazole, simeconazole, triadimefon, triadimenol,uniconazole, mancozeb, maneb, metiram, zineb, fludioxonil,fluquinconazole, difenoconazole,4,5-dimethyl-N-(2-propenyl)-2-(trimethylsilyl)-3-thiophenecarboxamide(sylthiopham), hexaconazole, etaconazole, triticonazole, flutriafol,epoxiconazole, bromuconazote, tetraconazole, myclobutanil, bitertanol,pyremethanil, cyprodinil, tridemorph, fenpropimorph, kresoxim-methyl,azoxystrobin, ZEN90160™, fenpiclonil, benalaxyl, furalaxyl, metalaxyl,R-metalaxyl, orfurace, oxadixyl, carboxin, prochloraz, triflumizole,pyrifenox, acibenzolar-S-methyl, chlorothalonil, cymoxanil,dimethomorph, famoxadone, quinoxyfen, fenpropidine, spiroxamine,triazoxide, BAS50001F™, hymexazole, pencycuron, fenamidone, guazatine,benomyl, captan, carbendazim, capropamid, ethirimol, flutolanil,fosetyl-aluminum, fuberidazole, hymexanol, kasugamycin,iminoctadine-triacetate, ipconazole, iprodione, mepronil, metalaxyl-M(mefenoxam), nuarimol, oxine-copper, oxolinic acid, perfurazoate,propamocarb hydrochloride, pyroquilon, quintozene, silthiopham, MON™65500, tecnazene, thiabendazole, thifluzamide, thiophenate-methyl,thiram, tolclofos-methyl, triflumizole, or any combination thereof. 14.The bioactive cationic polymer latex according to claim 1, comprisingfrom about 20 percent to about 99.5 percent by weight of theethylenically unsaturated first monomer, based on the total monomerweight.
 15. The bioactive cationic polymer latex according to claim 1,comprising from about 0.01 percent to about 75 percent by weight of theethylenically unsaturated second monomer, based on the total monomerweight.
 16. The bioactive cationic polymer latex according to claim 1,comprising from about 0.01 percent to about 40 percent by weightbioactive additive, based on the total monomer weight.
 17. The bioactivecationic polymer latex according to claim 1, comprising from 0 percentto about 25 percent by weight sterically bulky component, based on thetotal monomer weight.
 18. The bioactive cationic polymer latex accordingto claim 1, further comprising a nonionic surfactant.
 19. The bioactivecationic polymer latex according to claim 1, wherein the latex polymeris substantially devoid of cationic and anionic surfactants.
 20. Acoating comprising the bioactive cationic polymer latex according toclaim
 1. 21. An article comprising the bioactive cationic polymer latexaccording to claim
 1. 22. A method of making a bioactive cationicpolymer latex comprising initiating an emulsion polymerization of anaqueous composition comprising, at any time during the emulsionpolymerization: a) at least one ethylenically unsaturated first monomer;b) at least one ethylenically unsaturated second monomer that iscationic or a precursor to a cation; c) at least one bioactivecomponent; d) at least one free-radical initiator; e) optionally, atleast one sterically bulky ethylenically unsaturated third monomer; f)optionally, at least one sterically bulky polymer; and g) optionally, atleast one non nonionic surfactant.
 23. The method of making a bioactivecationic polymer latex according to claim 22, wherein the method is asemi-continuous process, and wherein at least one bioactive component isdissolved in the monomer feed at any time during the emulsionpolymerization.
 24. The method of making a bioactive cationic polymerlatex according to claim 22, wherein the method is a batch process, andwherein the at least one bioactive component is present in the seedstage of the emulsion polymerization.
 25. The method of making abioactive cationic polymer latex according to claim 22, wherein theaqueous composition components and the at least one bioactive componentare provided as a dispersion prior to initiating the emulsionpolymerization.
 26. The method of making a bioactive cationic polymerlatex according to claim 22, wherein the at least one ethylenicallyunsaturated first monomer is selected independently from a vinylaromatic monomer, a halogenated or a non-halogenated olefin monomer, analiphatic conjugated diene monomer, a non-aromatic unsaturated mono- ordicarboxylic ester monomer, a monomer based on the half ester of anunsaturated dicarboxylic acid monomer, an unsaturated mono- ordicarboxylic acid monomer, a nitrile-containing monomer, a cyclic or anacyclic amine-containing monomer, a branched or an unbranched alkylvinyl ester monomer, a halogenated or non-halogenated alkyl acrylatemonomer, a halogenated or non-halogenated aryl acrylate monomer, acarboxylic acid vinyl ester, an acetic acid alkenyl ester, a carboxylicacid alkenyl ester, a vinyl halide, a vinylidene halide, or anycombination thereof, any of which having up to 20 carbon atoms.
 27. Themethod of making a bioactive cationic polymer latex according to claim22, wherein the at least one ethylenically unsaturated first monomer isselected independently from styrene, para-methyl styrene, chloromethylstyrene, vinyl toluene, ethylene, butadiene, methyl(meth)acrylate,ethyl(meth)acrylate, propyl(meth)acrylate, butyl(meth)acrylate,pentyl(meth)acrylate, glycidyl(meth)acrylate, isodecyl (meth)acrylate,lauryl(meth)acrylate, monomethyl maleate, itaconic acid,(meth)acrylonitrile, (meth)acrylamide, N-methylol (meth)acrylamide,N-(isobutoxymethyl)(meth)acrylamide, vinyl neodecanoate, vinylversatates, vinyl acetate, a C₃-C₈ alkyl vinylether, a C₃-C₈ alkoxyvinylether, vinyl chloride, vinylidene chloride, vinyl fluoride,vinylidene fluoride, trifluoroethylene, tetrafluoroethylene,chlorotrifluoroethylene, hexafluoropropylene, chlorotrifluoroethylene,perfluorobutyl ethylene, a perfluorinated C₃-C₈ alpha-olefin, afluorinated C₃-C₈ alkyl vinylether, a perfluorinated C₃-C₈ alkylvinylether, a perfluorinated C₃-C₈ alkoxy vinyl ether, or anycombination thereof.
 28. The method of making a bioactive cationicpolymer latex according to claim 22, wherein the at least oneethylenically unsaturated second monomer is selected independently froman amine monomer, an amide monomer, a quaternary amine monomer, aphosphonium monomer, a sulfonium monomer, or any combination thereof,any of which having up to 20 carbon atoms.
 29. The method of making abioactive cationic polymer latex according to claim 22, wherein the atleast one ethylenically unsaturated second monomer is selectedindependently from dimethylaminoethyl acrylate; diethylaminoethylacrylate; dimethyl aminoethyl methacrylate; diethylaminoethylmethacrylate; tertiary butylaminoethyl methacrylate; N,N-dimethylacrylamide; N,N-dimethylaminopropyl acrylamide; acryloyl morpholine;N-isopropyl acrylamide; N,N-diethyl acrylamide; dimethyl aminoethylvinyl ether; 2-methyl-1-vinyl imidazole; N,N-dimethyl-aminopropylmethacrylamide; vinyl pyridine; vinyl benzyl amine; dimethylaminoethylacrylate, methyl chloride quarternary; dimethylaminoethyl methacrylate,methyl chloride quarternary; diallyldimethylammonium chloride;N,N-dimethylaminopropyl acrylamide, methyl chloride quaternary;trimethyl-(vinyloxyethyl)ammonium chloride;1-vinyl-2,3-dimethylimidazolinium chloride; vinyl benzyl aminehydrochloride; vinyl pyridinium hydrochloride; or any combinationthereof.
 30. The method of making a bioactive cationic polymer latexaccording to claim 22, wherein the at least one sterically bulkycomponent is selected independently from at least one sterically bulkyethylenically unsaturated third monomer, at least one sterically bulkypolymer, or any combination thereof.
 31. The method of making abioactive cationic polymer latex according to claim 22, wherein the atleast one sterically bulky component is at least one a sterically bulkyethylenically unsaturated third monomer selected independently from: a)CH₂═C(R^(1A))COO(CH₂CHR^(2A)O)_(m)R^(3A), wherein R^(1A), R^(2A), andR^(3A) are selected independently from H or an alkyl group having from 1to 6 carbon atoms, inclusive, and m is an integer from 1 to 30,inclusive; b) CH₂═C(R^(1B))COO(CH₂CH₂O)_(n)(CH₂CHR^(2B)O)_(p)R^(3B),wherein R^(1B), R^(2B), and R^(3B) are selected independently from H oran alkyl group having from 1 to 6 carbon atoms, inclusive, and n and pare integers selected independently from 1 to 15, inclusive; c)CH₂═C(R^(1C))COO(CH₂CHR^(2C)O)_(q)(CH₂CH₂O)_(r)R^(3C), wherein R^(1C),R^(2C), and R^(3C) are selected independently from H or an alkyl grouphaving from 1 to 6 carbon atoms, inclusive, and q and r are integersselected independently from 1 to 15, inclusive; or d) any combinationthereof.
 32. The method of making a bioactive cationic polymer latexaccording to claim 22, wherein the at least one sterically bulkycomponent is at least one sterically bulky ethylenically unsaturatedthird monomer selected independently from: a)CH₂═C(R^(1A))COO(CH₂CHR^(2A)O)_(m)R^(3A), wherein R^(1A), R^(2A), andR^(3A) are selected independently from H or methyl, and m is an integerfrom 1 to 10, inclusive; b)CH₂═C(R^(1B))COO(CH₂CH₂O)_(n)(CH₂CHR^(2B)O)_(p)R^(3B), wherein R^(1B),R^(2B), and R^(3B) are selected independently from H or methyl, and nand p are integers selected independently from 1 to 10, inclusive; c)CH₂═C(R^(1C))COO(CH₂CHR^(2C)O)_(q)(CH₂CH₂O)_(r)R^(3C), wherein R^(1C),R^(2C), and R^(3C) are selected independently from H or methyl, and qand r are integers selected independently from 1 to 10, inclusive; or d)any combination thereof.
 33. The method of making a bioactive cationicpolymer latex according to claim 22, wherein the at least one stericallybulky component is selected independently from: an alkoxylated monoesterof a dicarboxylic acid; an alkoxylated diester of a dicarboxylic acid; apolyoxyethylene alkylphenyl ether; a polymerizable surfactant; or anycombination thereof.
 34. The method of making a bioactive cationicpolymer latex according to claim 22, wherein the at least one stericallybulky component is at least one sterically bulky polymer selectedindependently from polyvinyl alcohols, polyvinyl pyrollidone,hydroxyethyl cellulose, or any combination thereof.
 35. The method ofmaking a bioactive cationic polymer latex according to claim 22, whereinthe at least one bioactive component is selected independently fromundecylenic acid; undecylenic alcohol; the reaction product ofundecylenic acid with hydroxylethyl(meth)acrylate or polyethylene glycol(meth)acrylate; the reaction product of undecylenic alcohol with(meth)acrylic acid, maleic anhydride, or itaconic acid; chitosan ormodified chitosans; or any combination thereof.
 36. The method of makinga bioactive cationic polymer latex according to claim 22, wherein the atleast one bioactive component is selected independently from copper,copper salts, silver, silver salts, zinc, zinc salts, silver oxide, zincoxide, chlorhexidine, chlorhexidine gluconate, glutaral, halazone,hexachlorophene, nitrofurazone, nitromersol, povidone-iodine,thimerosol, C₁- to C₅-parabens, hypochlorite salts, clofucarban,clorophene, poloxamer-iodine, phenolics, mafenide acetate, aminacrinehydrochloride, quaternary ammonium salts, oxychlorosene, metabromsalan,merbromin, dibromsalan, glyceryl laurate, pyrithione salts, sodiumpyrithione, zinc pyrithione, (dodecyl)(diethylenediamine)glycine,(dodecyl)(aminopropyl)glycine, phenol, m-cresol, o-cresol, p-cresol,o-phenyl-phenol, resorcinol, vinyl phenol, polymeric guanidines,polymyxins, bacitracin, circulin, octapeptins, lysozmye, lysostaphin,cellulytic enzymes, vancomycin, ristocetin, actinoidins, avoparcins,tyrocidin A, gramicidin S, polyoxin D, tunicamycin, neomycin,streptomycin, or any combination thereof.
 37. The method of making abioactive cationic polymer latex according to claim 22, wherein the atleast one bioactive component is selected independently fromazaconazole, biternatol, bromuconazole, cyproconazole, diniconazole,fenbuconazole, flusilazole, flutnafol, imazalil, imibenconazole,metconazole, paclobutrazol, perfuazoate, penconazole, simeconazole,triadimefon, triadimenol, uniconazole, mancozeb, maneb, metiram, zineb,fludioxonil, fluquinconazole, difenoconazole,4,5-dimethyl-N-(2-propenyl)-2-(trimethylsilyl)-3-thiophenecarboxamide(sylthiopham), hexaconazole, etaconazole, triticonazole, flutriafol,epoxiconazole, bromuconazote, tetraconazole, myclobutanil, bitertanol,pyremethanil, cyprodinil, tridemorph, fenpropimorph, kresoxim-methyl,azoxystrobin, ZEN90160™, fenpiclonil, benalaxyl, furalaxyl, metalaxyl,R-metalaxyl, orfurace, oxadixyl, carboxin, prochloraz, triflumizole,pyrifenox, acibenzolar-S-methyl, chlorothalonil, cymoxanil,dimethomorph, famoxadone, quinoxyfen, fenpropidine, spiroxamine,triazoxide, BAS50001F™, hymexazole, pencycuron, fenamidone, guazatine,benomyl, captan, carbendazim, capropamid, ethirimol, flutolanil,fosetyl-aluminum, fuberidazole, hymexanol, kasugamycin,iminoctadine-triacetate, ipconazole, iprodione, mepronil, metalaxyl-M(mefenoxam), nuarimol, oxine-copper, oxolinic acid, perfurazoate,propamocarb hydrochloride, pyroquilon, quintozene, silthiopham, MON™65500, tecnazene, thiabendazole, thifluzamide, thiophenate-methyl,thiram, tolclofos-methyl, triflumizole, or any combination thereof. 38.The method of making a bioactive cationic polymer latex according toclaim 22, wherein the bioactive cationic polymer latex comprises fromabout 20 percent to about 99.5 percent by weight of the ethylenicallyunsaturated first monomer, based on the total monomer weight.
 39. Themethod of making a bioactive cationic polymer latex according to claim22, wherein the bioactive cationic polymer latex comprises from about0.01 percent to about 75 percent by weight of the ethylenicallyunsaturated second monomer, based on the total monomer weight.
 40. Themethod of making a bioactive cationic polymer latex according to claim22, wherein the bioactive cationic polymer latex comprises from about0.01 percent to about 40 percent by weight bioactive additive, based onthe total monomer weight.
 41. The method of making a bioactive cationicpolymer latex according to claim 22, wherein the bioactive cationicpolymer latex comprises from 0 percent to about 25 percent by weightsterically bulky component, based on the total monomer weight.
 42. Themethod of making a bioactive cationic polymer latex according to claim22, wherein the bioactive cationic polymer latex is substantially devoidof cationic and anionic surfactants.
 43. A method of making a bioactivecationic polymer latex comprising: a) providing an aqueous compositioncomprising: i) at least one ethylenically unsaturated first monomer; ii)at least one ethylenically unsaturated second monomer that is cationicor a precursor to a cation; iii) optionally, at least one stericallybulky ethylenically unsaturated third monomer; iv) at least onefree-radical initiator; and v) optionally, at least one non-ionicsurfactant; b) initiating an emulsion polymerization of the composition;and c) adding at least one bioactive component to the composition duringthe emulsion polymerization process.